Recovery of boron fluoride



May 1s, 195o G. N. CADE 2,507,499

l REcovERY oF BoRoN FLuonIDE Filed sept. 2s, 1946 ATTORNEYS Patented May 16, 1950 RECOVERY F BORON FLUORIDE George N. Cade, Bartlesville, Okla., asslgnor to Phillips Petroleum Company, a corporation of Delaware Application September 23, 1946, Serial No. 698,747

(Cl. 26o-683.4)

12 Claims.

This invention relates to the recovery of boron. In a specific embodiment the invention relates to recovering boron from organic material. One aspect of the invention relates to the treatment of hydrocarbons or other organic reactants with catalysts or treating agents comprising a boron halide under such conditions that some boron becomes incorporated in a complex with `the organic material, and to the treatment of the resulting complex to recover the boron content thereof in the form of la boron halide which can then be reused in the process. One feature of the invention relates to hydrocarbon conversion processes effected in the presence of a catalyst comprising boron triiluorlde, hydrogen fluoride.

and relatively minor amounts of water; acld-soluble oils are recovered from the catalyst and treated to recover boron therefrom, in the form of an admlxture of boron fluoride, hydrogen fluoride and water which is recycled to the conversion as catalyst.

The use of concentrated hydrogen fluoride as catalyst for effecting many organic reactions has increased greatly in recent years. It has been found in many instances that the use of a minor proportion of boron iluoride with the hydrogen fluoride greatly increases the catalytic activity and/or the selectivity of the catalyst. It has likewise been found that for certain reactions at least, the catalyst may also comprise water in amounts ranging from traces up to 30% or more. Another useful catalyst is composed of boron fluoride and water alone, commonly termed boron uoride hydrate, and ordinarily prepared by saturating water with boronuorlde at near-atmospheric temperatures.

Among the reactions which are catalyzed by hydrogen fluoride and/or boron fluoride may be mentioned the alkylation of aromatic compounds with various alkylating reactants including ole ins, alcohols, alkyl halides, etc. Paraillnic and cycloparafllnic (naphthenic) hydrocarbons may also be alkylated with such catalysts and such alkylating reactants. Furthermore, various hydrocarbons, particularly parafllnic hydrocarbons, may be isomerized; ordinarily one isomer is converted to a corresponding branched or more branched isomer although the reverse reaction may be accomplished if desired. The esteriiication reaction between organic acids and alcohols,

and the` etheriflcation reaction between alcohols and alkyl halides, may also be mentioned as examples of reactions catalyzed by HF and/or BFa.'

of both lower and higher molecular weights aro concomitantly formed. It will be appreciated that particular catalyst compositions which are effective for one type of conversion will not necessarily be equally eilective for another conversion, and may in some cases be completely incapable of eiecting a diierent conversion. Suitable catalyst compositions for any particular reaction are well known in the art, and hence need not be discussed here in further detail. Mixtures of boron fluoride and hydrogen fluoride have likewise been employed as solvents for removing sulfur compounds, oxygen compounds and unsaturated compounds 'from hydrocarbons or other organic materials.

When catalysts or treating agents of the foregoing nature are contacted with organic compounds, materials known as acid-soluble oils are formed. These oils are of a complex nature and contain organic material as well as boron and fluorine in combined form. The exact nature of the acid-soluble oils and the manner in which the boron and the iluorine are combined with the organic material are not clearly understood. Prob- -ably some boron uoride-hydrocarbon complexes are present, and substantial amounts of fluorine are present in the form of organic -uorides. Accumulation of acid-soluble oils in the catalyst or treating agent lowers the eiiiciency thereof, and it is necessary to separate acid-soluble oils from the bulk of the catalyst or treating agent either intermittently or continuously. This may readily be done by distillation or vaporization of the boron fluoride, HF, or water, leaving a residue of acidsoluble oils. The latter are ordinarily discarded and accordingly represent serious losses of boron and fluoride.

It is an object of this invention to recover boron from organic material containing boron in combined form.

It is another object of the invention to subject acid-soluble oils, resulting from use of boron halide-containing catalysts or treating agents to eilect organic reactions or treat organic materials, to a treatment effective in recovering the boron content in a form suitable for reuse in the process.

Still another object is to subject hydrocarbons to conversion in the presence of a catalyst comprising boron fluoride, hydrogen fluoride, and water.

A still 'further object of the invention is to reduce the consumption of boron fluoride in proc esses of the nature described.

Yet another object is to subject boron-containing materials to a step-wise treatment resulting ln the production of a BFa-HF--HaO mixture having catalytic activity.

Other objects and advantages of the invention will be apparent, to one skilled in the art, from the accompanying disclosure and discussion.

My invention -will be described with particular reference to the disproportionation of a paraln hydrocarbon, speciiically normal pentane. It will, of course, be understood that the principles disclosed herein may likewise be applied, with suitable modifications where necessary, to other types of conversion or treating processes, including those of the nature described above.

In a .preferred embodiment of the invention an acid-soluble oil, recovered trom a catalyst comprising hydrogen iiuoride plus minor propor tions of boron fluoride and water. is subjected to complete oxidation to convert the boron content thereof to boron oxide. The acid-soluble oil may rst be heated to drive oiI aportion of the boron in the form of boron triuoride. The boron oxide formed as just described is next reactedy with concentrated hydrogen fluoride, which is preferably used in large excess, to .produce a resulting mixture of hydrogen fluoride, boron iiuorlde, and water, the principal reaction apparently being the formation of boron fluoride and water in accordance with the following equation:

The resulting mixture is then recycled for incorporation in the main body of the catalyst. The procedure will be described in more detail below in conjunction with the drawing. Y

The present invention is; particularly .eicctlv in conjunction with the reeoi'istructionV of lwdrocarbons. It has been shown that in the presence of substantial proportions of hydrofiuoric acid. and under suitable conditions of time and temperature, saturated hydrocarbons are reconstructed to hydrocarbons of different carbonskeleton arrangement and different boiling point. Parafnic hydrocarbons, for example, undergo conversion to isomers and also undergo conversion to hydrocarbons of both lower and higher molecular weights and correspondingly lower and higher boiling temperatures. It was later found that a marked improvement in the emciency and utilization of concentrated hydroiluoric acid as a catalyst for reconstructing hydrocarbons is brought about by including with it a minor proportion of boron iiuoride. As disclosed in the copending application of Frederick E. Frey, Serial No. 511,444, Patent No. 2,461,541, nled November 23, 1943, hydrocarbons, preferably saturated hydrocarbons such as the parains and cycloparains, are treated with concentrated hydrouoric acid which contains or which has added to it a minor proportion of boron iiuoride, to produce other hydrocarbons. As further disclosed in said application of Frederick E. Frey, the catalyst may be improved by the addition of a small amount of water, which will be discussed in more detail herein below. By simple modiiications of the hydrocarbon reconstruction process, paraiiln hydrocarbons may be converted to other parafn hydrocarbons isomeric with the paranlns treated; furthermore, paraflln hydrocarbons may be converted to other paraflln hydrocarbons having more and/or fewer carbon atoms per molecule; likewise, cycloparamns may be converted to other cycloparains having different alkyl groups and/or a different number of carbon atoms in the ring. In carrying out the process, it appears that two types of reaction occur. One of these reactions is true isomerization as when normal butane is converted to isobutane, normal pentane to isopentane, methylcyclopentane to cyclohexane and the like. and also the reverse of these reactions. The other reaction which appears to be involved is primarily one of disproportionation, as when normal pentane is converted to more or less equlmolar amounts oi butanes and hexanes with the iso compounds generally predominating. In many instances these two types of reactions take place concurrently with the formation of products which'include isomers of the original hydrocarbons treated and hydrocarbons having fewer and greater numbers of carbon atoms per molecule. However, in most cases the reaction conditions may be controlled particularly with the inclusion of modifying agents, to vary the ratio of these reaction types. The process is directed primarily to converting low-boiling saturated hydrocarbons having at least four carbon atoms per molecule and boiling below about 450 F., although at times saturated hydrocarbons boiling outside this range may be treated.

The different types of reactions which are be lieved to be involved in the reconstruction of saturated hydrocarbons in accordance with `the process .may be exempliiied as follows:

(l) 205111: S 01H14 -l- 04H10 (pantanos) (berlines) (butanes) (a) n-heptane t; branched heptanes (b) n-butane t; isobutane 00H12 S CHiCsHt (eyclohexane) (methylcyclopentane) Although several other types of reaction probably also take place in the reconstruction process, the above mentioned types appear to account for most of the effects which are produced. The general term "reconstruction is used herein to denote the production of one or more of the above mentioned effects and/or other advantageous effects which result from the practice of the process.

The catalyst employed comprises a major proportion of hydrouoric acid modified or activated by a minor proportion of boron triuoride. No nickel or other additional catalytic agent is required, and in many cases the reactions may be carried out at normal atmospheric temperature or at a temperature only somewhat higher than atmospheric temperature. In its preferredl form, the catalyst comprises a homogeneous liquid solution of boron iiuoride in a large excess of liquid hydroiiuoric, acid. (In determining the so-called K constants" of so lutions of boron trifluorlde in liquid anhydrous hydrofluoric acid it has been determined that there appears to be primarily a true solution of boron trifluoride in the liquid hydro iiuoric acid.) However, in certain reactions, an induction period has been observed which, in certain instances, has been eliminated by the addition of reactive hydrocarbons, such as olens. Also, complexes between hydrocarbons and the catalyst ingredients have been found in the catalyst phase after use. In a still further preferred modincation there is included in this catalytic mixture a small amount of Water since, as will be shown hereinafter, the use of strictly anhydrous hydronuoric acid and a minor amount of boron triuoride as the catalyst is accompanied by the formation of an appreciable amount of sludge. This sludge does not make the use of an anhydrous catalvst impractical or uneoonomical but, as can readily'be appreciated.

fluoride through -conduit 14.

is undesirable. It has been found thatwhen the catalyst is not strictly anhydrous, but contains a small amount oi Watan-there is a much. smaller amount of sludge formed.

The accompanying drawing is a schematic iiow diagramshowing one arrangement of apparatus elements and flow of materials therethrough.,

suitable for the practice of my invention as applied to a pentane disproportionation system. It will readily beappreciated that the representation in the drawing is diagrammatic in nature, and that, for the sake of simplicity, many conventional items such as valves, pumps, heat exchangers, automatic controls, and the like are not shown, inasmuch as their nature and use is well understood to those skilled in the art.

In the drawing, normal pentane enters reactor Il through conduit 8 and is intimately mixed with the catalyst which enters through yconduit 3. The catalyst comprises liquid hydrofiuoric acid containing from 0.1 to 10 gweightper cent boron iiuoride plus small amounts of water. Hydrogen fluoride may be introduced through conduit 12, waterthrough conduit 13, and boron Although the amount of boron triuoride may be as much as about to 30% by weight of the hydrouoric acid, it is found that with pentane as the reactant there is little benefit to be derived by use of more than 10% Bli'a.v Substantially more drastic reaction conditions are necessary in effecting the reconstruction of butane, which ordinarilyrequires greater amounts of boron tri-v fluoride together with somewhat highertemperatures and longer reaction times.

The concentration of water inv the reactor should be at least about 0.05% by weight of the HF-BFa catalyst and generally need not exceed about 1.0% by weight although in some instances higher concentrations may be found to be desirable. However, the amount of water used should not exceed the molecular equivalent of boron trifluoride present since apparently the water disappears as such through the formation of a complex with the boron triuoride and an appreciable amount' of free boron trifluoride must be present to effect the reconstruction reactions at a desirably rapid rate in the preferred temperature range. The percentages of boron triiiuoride mentioned above referred to the amount of free boron trifluoride present over and above that which is molecularlyv equivalent to the water content of the catalyst.

In reactor l0 normall pentane. is convertedA to a mixture of hydrocarbons comprising butanes, isopentane, hexanes, and heavier hydrocarbons, in addition to Asmaller amounts of propane and lighter. Conditions generally suitable for the reaction are: temperature, 70 to 200 F.; pressure, sufficient to maintainthe reactants in the liquid phase; volume ratio of hydrocarbon to catalyst, about 1:1; reaction time, 5 minutes to one hour. The reaction is preferably conducted continuously, although batch operation may be employed if desired. Reactor I0 may take the form of a pressure vessel agitated with suitable paddles or internal pumps or other arrangements well known to the art.

After a suitable reaction time, the hydrocarboncatalyst mixture is passed through conduit to settler 20 in which it separates into a heavy catalyst phase and a light hydrocarbon phase. The hydrocarbon phase is passed through conduit 23 to a fractionation system indicated diagrammatically by fractionation zone 30. 'Ihis in ordinary equipment. vhydroiluoricacid and boron trifluoride dissolvedv practice will comprise aseries of two or more fractional distillation columns and associated A light fraction comprising the in the hydrocarbon phase together with propane is recovered'through line 3|. Components of this fraction may be separated and recycled if desired by means vnot shown in the drawing. The propane and any lighter hydrocarbons may be passed (by means not shown) to 'subsequent' utilization in the boron .recovery unit as described below. The butane fraction, which is largely isobutane.

is recovered through line 32. The pentane fraction is recovered through line 33. Unreacted normal pentane is preferably separated and recycled to the reaction. A fractioncomprising branched chain hexanes and heavier hydrocarbons is recovered through outlet 34. The isobutane, isopentane; and hexanes and` heavier fractions are the desired products of the reconstruction process.

Most of the catalyst phase isrecycled from settler 20 via conduit 2| to the reactor |0 for reuse as' catalyst. A portion, however, is withdrawn intermittently or continuously through conduit 22 to catalyst vfractionation system 40 for purification and recovery of boron and fiuorine therefrom.I Unit,40 ordinarily comprises one or two fractional distillation columns and related equipment and may also comprise one or more simple flash chambers or drums.l Acid-resistant alloys may be employed in the manufacture of this equipment or at least in that portion which comes in contact'with highly corrosive concentrations of aqueous lhydrofiuoric acid. A llowboilingffraction comprising substantially anhydrous HF and a minor proportion of BF; is withdrawn from unit 40 via conduit 4| and'is recycled .to reactor I0 via conduits 65 and 9. Any undesirably high excess of water which `may accumulate inthe catalyst phase yis withdrawn as desired through the outlet 42 as a fraction comprising water and HF, usually' in azeotropic proportions. A residue comprising acid-soluble oils is recovered through conduit 43. vThe oil may be passed via. conduit and 69) to storage 45 if desired. v

The acid-soluble oils are preferably passed into unit-10 equipped with heater 68 and subjected therein to elevated temperatures for a suihcient time to recover a substantial part of the com bined boron and fluorine contained therein in the form of BH3 and HF which may be returned to the reactor by means of lines 61, 4|, 65 and 9.A Appreciable amounts of hydrocarbon materials may also Ibe recovered in this man-ner. It is often impossible, however, to recover all of the boron present in the acid-soluble oils by simple heating even though extremely high temperatures are used, as is shown in Example I below. In accordance with my invention, therefore, the residue which is passed via line 69 into storage 45 is subjected to treatment for recovery of boron. Preferably a hydrocarbon such as propane is introatomes l means IS through conduit 48 provided with valve 41 tocombustion chamber 50, in which it is substantially completely burned in the presence oi air or other oxygen-containing gas which-is introduced through inlet 48 provided with valve I9. Combustion chamber 50 maybe of any suitable design so long as it is provided with a burner suitable for handling heavy oils. The combustion products, which comprise chiefly boric oxide, 'car" bon dioxide, and steam, are passed through conduit I to cooling zone 52 in which they are 'rapidly cooled to a tempera-ture in the range of about 400 to 900 F. in order to cause the boric oxide to separate as a solid suspended in combustion gases. The velocity of the combustion 'gases through combustion chamberlii and cooling unit 52 is preferably suiliciently high to minimize deposition of boric oxide. The cool combustion products are passed vla conduit 53 intoseparator i0, which includes conventionalapparatus for separating solids from gases, such as a cyclone separator, bag ii1ter, 'Cottrell precipitator, or a combination of two or more of these devices. The combustion gases are withdrawn through outlet il equipped with valve 62.-

When a suitable amount of boric oxide has accumulated in separator 60, valves "A, 41, 58 and 62 are closed and valves 64 and 66 are opened. s

Concentrated hydroiiuoricacid, preferably anhydrous, is passed through inletconduit 63 into separator Sli, and dissolvesV the accumulated boric oxide, converting it to boron fluoride and water. The amount of hydroiluoric acid added ispreierably about 5 to 30 times the amount theoretical ly required to eiect complete conversion in accordance with the equation:

swimwear-Manso The large excess of hydroiluoric acid is used with the aim of promoting the completionof the refractionation system, rather than to sommaire with the total catalyst in the reactor, so that' water maybe removed through line l2. In conversions in which an excess of water can be tolerated these'procedures may not be necessary.

It may often be desirable to introduce the hydrogen iiuoride which is to dissolve the boric oxide into combustion chamber' Ec and/or cooling zone 52 in order to dissolve accumulated deposits of boric oxide. The resulting material may then be passed o n through separator GQ to dissolve boric oxide `accumulated therein. Temperatures oi about to 100 C. are adequate tor the Bios-#HF reaction. 1 v

.It will be understood by' those skilled in the art that the presentfinvention may be practiced by arrangements oi apparatus other than that shown diagrammatically in the'drawing. For cx-y ample, combustion chamber 60,'cooling Ilione I2,

action and minimizing formation of intermediate acids containing boron, iiuorine, and. engen. The excess hydrogen fluoride also results in the formation of a total reaction mixture in which HF is the major component and BFa and water are present in relatively smallamounts, thus corresponding approximately to the composition of the catalyst. Accordingly; the total reaction mixture is recycled through conduit 65 to reactor I0 where it'becomes incorporated with the catalyst. In conversions such as the disproportionation reaction described herein, in which boron -uoride should be'present in molecular excess over the water, it usually results that the quantity of makeup boron uoride introduced' through conl and separator Slimay' be comblned in a single piece of apparatus, somewhat similar to the type commonly used in preparing channel black,` in which the acid-soluble oil is burned and the combustion products impinge against cooled balles. which are subsequently sprayed with liquid anhydrous hydroiluoric acid to remove and recover the deposited solid boric oxide. Furthermore,A

the recoveryoperation may be made substantially continuous by using a standnby combustion chamber, cooling -zone, land separator, identical with those represented in the drawing by the numerals 5t, 52, and 60, respectively, in which the combustion and the boric oxide separation are con-l ducted while the accumulated boric oxide in sep?. arator 6 9 is being-treated lwith hydroiluoric racid` as previously described.

The following examples are given to illustrate certain `features .of the invention. It will, oi'

course, be understood that the invention in its broad scope is not necessarily limited to the particular conditions disclosed in the examples.

i EXAMPLE: k Several different hydrocarbon conversion reactions catalyzed by liquid anhydrous hydrouoric acid containing from 2 to 3 weight per cent boron.

` iluoride were conducted. Part of the used catalyst from each reaction was evaporated at room temperature, and the acidsoluble oil which remained as a residue was heated for several hours at an elevated temperature. The boron content of the oil was then determined. The data ohtallied are given in the table:

duit 'I4 is adequate t'o maintain-,this excess overthe water formed in the reaction between the boricoxide and HF. -Howeven in the-event that boron fluoride makeup is insuillcient to maintain the desired excess, water may be removed from the system -by any suitable method, for example, as an HF-water azeotropeirom catalystfracsary to maintain the desired Blas-H20 ratio in the system.A In another modiiication, sometimes preferred,"the used catalyst is distilled to remove uonator 4u through une 42, to the extent oeoesf acid-soluble oil, and the oil-free fraction or .a portion thereof is 'distilled in the presence. of

sulfuric acid to remove water. Another method isto distill the BFz-HnC-HF reaction product mixture resulting from reaction of boric oxide with excess in the presence of sulfuric acid to recover BF: 'and/or HF with a substantially reduced water content. If desired, the reaction product mixture may .be passed to the catalyst Isobutane was alkylated with ethylene at 127 F. and 206 p. s. i. The mol ratio of isobutane to ethylene was 5.44. The catalyst used consisted of 96.9 parts by weight anhydrous hydrogen fluoride and 3.1 parts -by weight boron triiluoride, plus a small amount of water'and acid-soluble oils. The

product was principally branched-chain hexanes, in which diisopropyl predominated. An aliquot portion of the used catalyst was evaporated at room temperature, and the acid-soluble oil, which remained as a residue, was heated at 302 F. for several hours. A sample of theremaining oil was then analyzed and found to contain 4.8' weight per cent boron, which corresponded to 24 per cent of the boron fluoride charged.

The acid-soluble oil which had been thus heated was dissolved in octane and burned in an atmosphere of oxygen. Combustion was substantially complete, and the boron content of the oil was converted to boric oxide.

In a continuous alkylation process, the boric oxide is separated from the other combustion products and is reacted with 20 times its weight of anhydrous hydroiluoric acid. The mixture so obtained is recycled directly to the alkylation step. Boron nuoride consumption is thus substantially reduced and suillcient water is supplied by the reaction between HF' and boric oxide to maintain the small amount of water desired in the catalyst.

Various modifications may be made in the procedures and conditions disclosed herein, as will be understood by one skilled in the art. In some cases, for instance, vit will be desired to recover from' admixture with hydrogen fluoride and water the boron fluoride produced by reacting boric oxide with hydrogen fluoride. This may be accomplished by distillation or otherwise, and the recovered boron iluoride utilized in any desired manner. While mixtures of boron tritluoride with hydrogen fluoride, and mixtures of boron trifluoride with hydrogen iluoride and water. are discussed herein as if the individual components retain their identity, it will be appreciated that this is not necessarily the case in all circumstances, and that such mixtures are believed in many instances to be rather complex in nature. Accordingly, by terms such as mixture of boron fluoride with hydrogen fluoride,

or the like, as used in the description and claims, are meant to be included all materials which may result from mixing the compounds named, and all materials which are substantially the same as materials which can be prepared by such mixing. Forinstance, when boric oxide is reacted with an excess of hydrogen fluoride, it may be that boron fluoride and water as such are not the only products, but the nal total reaction product has approximately the same properties as a material which can be prepared by mixing HF, BFs, and H2O in the required proportions.

I claim: l

1. In the conversion of organic materials by means of a catalyst consisting essentially of boron triiluoride and hydrogen fluoride as the catalytic components thereof wherein an acid-soluble boronand fiuorine-containing oil is formed as by-product, the improvement which comprises separating said acid-soluble oil from the bulk of the catalyst, oxidizing so-separated acid-soluble oil to form boric oxide, reacting said boric oxidev with hydrogen uoride to form a BFs-HF--HzO mixture, and using said mixture as at least part of the catalyst for the conversion.

2. In the conversion of hydrocarbons by means of a BFa-HF-HzO catalyst wherein an acidsoluble boronand uorine-contaimng oil is formed as by-product, the improvement which comprises separating said acid-soluble oil from the bulk of the catalyst, burning so-separated acid-soluble oil in an oxygen-containing gas to 1.0 form boric oxide, reacting said boric oxide with astoichiometric excess oi' HF to form a BFa-HF-HnO mixture and using same as at least part of the uble boronand iluorine-containing oil is formed as by-product, the improvement which comprises separating said acid-soluble oil from the bulk of the catalyst. heating so-separated acid-soluble oil at such an elevated temperature and for such a time as to eiect partial recovery of boron and iluorine therefrom in the form of a gas fraction comprising BF: and HF while leaving a liquid boron-containing residue, burning said liquid residue in an oxygen-containing gas to form boric oxide, reacting said boric oxide with HF to form a BFs-HF-HzO mixture, and using said BFs-HF--HRO mixture and BF; and HF contained in said gas fraction as at least part of the catalyst for the conversion.

5. A continuous process for the conversion of hydrocarbons which comprises continuously contacting in a reaction zone hydrocarbon reactant materials with a liquid catalyst comprising a minor proportion of boron triiluoride dissolved in liquid hydrogen nuoride together with a minor amount of water, continuously withdrawing a mixture of hydrocarbons and catalyst from said reaction zone and separating same into a hydrocarbon phase and a catalyst phase, recovering hydrocarbon reaction products from said hydrocarbon phase, continuously recycling the bulk of said catalyst phase to said reaction zone, passing a portion of said catalyst phase to a distillation zone and therein separating same into a boron trifiuoride-hydrogen uoride fraction and a heavier acid-soluble oil fraction containing boron and fluorine in combined form, returning said boron triiluorlde-hydrogen fluoride fraction to said reaction zone for incorporation in the catalyst, burning said acid-soluble oil fraction in an atmosphere of oxygen-containing gas, separating boric oxide from combustion gases, reacting said boric oxide with a large excess of concentrated hydrofluoric acid to form a mixture comprising a major proportion of hydrogen fluoride and minor proportions of boron trifluoride and water. and passing said mixture to said reaction zone for incorporation in the catalyst.

6. The process of claim 5 in which said acidsoluble oil fraction before burning is first heated at an elevated temperature to drive oil a portion of its boron and iluorine content in the form of boron triiluoride and hydrogen iluoride which are passed to the reaction zone for incorporation in the catalyst.

7. The process of claim 5 in which light hydrocarbon gases are separated from said hydrocarbon phase, and at least a portion of said light gases are admixed in the liquid state with said acid-soluble oil fraction, to assist the handling and burning of the acid-soluble oil.

8. The process of claim 5 in which said conversion is the reaction of an alkylatable hydrocarbon with an alkylating reactant to form branched-chain alkylated hydrocarbons 9. A process for the reconstruction oi' saturated hydrocarbons which comprises contacting in a reaction zone saturated hydrocarbons with a liquid catalyst comprising a minor proportion of boron triiluoride dissolved in' liquid hydrogen fluoride together with a minor amount of water, said boron triiiuoride being present in molar excess of said water, withdrawing a mixture of hydrocarbons and catalyst from said reaction zone and separating same into a hydrocarbon phase and a catalyst phase, recovering reconstructed saturated hydrocarbons from said hydrocarbon phase as a product of the process, returning the bulk of said catalyst phase to said reaction zone, passing a portion of said catalyst phase to a distillation acne and therein separating same into a light boron triuoride-nydrogen fluoride fraction and a heavy acid-soluble oil fraction containing boron and uorine in combined form, returning said boron triuoride-hydrogen uoride fraction to said reaction zone for incorporation in the catalyst, burning said acid-soluble oil fraction in an '12 water is separated trom the system by withdrawing a water-containing fraction from said distillation zone.

11. The process of claim 9 in which normal pentane is subjected to reaction conditions eiecting reconstruction of same to form isobutane. sgpentane, and hexane andheavier hydrocar- 12. The process of claim 9 in which excess water is separated from the system by distilling a water-containing -boron triiluoride-hydrogen fluoride mixture in the presence of sulfuric acid to dehydrate the mixture.

' GEORGE N. CADE.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 2,109,340 Nieuwland et ai. Feb. 22, 1938 2,135,454 McAlevy Nov. 1, 1938 2,296,370 Slotterbeck Sept. 22, 1942 2,339,248 Danforth Jan. 18, 1944 2,339,249 Danforth Jan. 18, 1944 2,363,116 Bruner Nov. 21, 1944 2,381,027 Balderschwieler et ai. Aug. 1, 1945 2,405,995 Burk Aug. 20, 1946 

1. IN THE CONVERSION OF ORGANIC MATERIALS BY MEANS OF A CATALYST CONSISTING ESSENTIALLY OF BORON TRIFLUORIDE AND HYDROGEN FLUORIDE AS THE CATALYTIC COMPONENTS THEREOF WHEREIN AN ACID-SOLUBLE BORON- AND FLUORINE-CONTAINING OIL IS FORMED AS BY-PRODUCT, THE IMPROVEMENT WHICH COMPRISES SEPARATING SAID ACID-SOLUBLE OIL FROM THE BULK OF 